1. Field of the Invention
The present invention relates generally to high performance polymers. The present invention relates particularly to polyimide copolymers with reactive endgroups that are useful as adhesives, composite matrices, moldings, films and coatings.
2. Description of Related Art
Wholly aromatic polyimides are known for their exceptional thermal, thermo-oxidative and chemical resistance, but are generally difficult to process as structural adhesives or composite matrices. Several polyimides such as Kapton.RTM. (DuPont), PI-2080 (Dow Chemical, licensed to Lenzing), XU-218 (Ciba-Geigy), Ultem.RTM. (General Electric) and LaRC.TM.-TPI (Mitsui Toatsu) are commercially available and used as fibers, films, moldings, adhesives or composite matrices.
Currently available equipment to process polyimides into useful parts are limited in their pressure and temperature capability, and certain applications require checkering of adhesives and composites with other structures such as foams or honeycombs. Because of the equipment limitations (especially autoclaves) and concuring requirements, it is extremely important to provide materials that are processable at 250 psi or below and 371.degree. C. or below. Because of the foams and honeycombs that are being proposed for use in some applications, reductions in pressure below 250 psi are also very significant.
While improved processing conditions are very important, the polyimides must also display better mechanical and adhesive properties to meet the needs of many future applications. Especially important for these applications are properties measured at temperatures of 177.degree. C. or slightly higher for use over long time periods at those elevated temperatures.
Thermoplastic polymers currently available are either difficult to process into high quality parts or have limited mechanical performance at the elevated temperatures for short or long periods of time. The related art that comes closest to meeting the needs of future applications is a thermoplastic polyimide known as LARC.TM.-IA, as described by St. Clair and Progar in U.S. Pat. No. 5,147,966. However, this polyimide requires higher processing conditions than desired and/or provides lower mechanical and adhesive properties than desired, depending on the tests performed.
The incorporation of ethynyl groups in polyimides has been reported in the literature, typically as terminal groups to yield acetylene-terminated imide oligomers (ATI). Therimid-600, an oligoimide with acetylene end groups was first developed at the Hughes Aircraft Co. [N. Bilow, A. L. Landis and L. J. Miller, U.S. Pat. No, 3,845,018 (1974); A. L. Landis, N. Bilow, R. H. Boschan, R. E. Lawrence and T. J. Aponyi, Polym. Prepr., 15, 537(1974); N. Bilow and A. L. Landis, Natl. SAMPE Tech. Conf. Ser., 8, 94(1976)]. Several reviews on polyimides or acetylene-terminated prepolymers are published and discuss other acetylene containing polyimides [P. M. Hergenrother, in (H. Mark, ed.) Encyclopedia of Polymer Science and Engineering, 2nd. ed., vol. 1, John Wiley and Sons, Inc., New York, 61(1985); P. M. Hergenrother in (H. Mark, ed.) Encyclopedia of Polymer Science and Engineering, 2nd. ed., vol. 7, John Wiley and Sons, Inc., New York, 639(1987); T. Takekoshi, in (C. G. Overberger, ed.) Advances in Polymer Science, 2(1990)]. Polyimides containing pendent ethynyl groups have been reported but one reference contains an abstract only with no experimental details or polymer properties [F. W. Harris, S. M. Padaki and S. Varaprath, Polym. Prep., 21(1 ), 3(1980)]. Another disclosure on polyimides containing pendent ethynyl groups contains detailed experimental information and polymer properties [B. J. Jensen, P. M. Hergenrother and G. Nwokogu, Polym, Prep., 33(1), 914 (1992) and B. J. Jensen, P. M. Hergenrother and G. Nwokogu, Polymer, 34(3), 630, (1993)].
Maleimide terminated polymers (bismaleimides) have been known for many years [G. F. D. Alelio, U.S. Pat. No. 3,929,713 (1975)]. They are a leading class of thermosetting polyimides because of their excellent processability and balance of thermal and mechanical properties, making them extremely popular in advanced composites and electronics. Many different bismaleimides have been synthesized with a variety of connecting groups between the maleimide rings [D. Wilson, H. D. Stenzenberger and P. M. Hergenrother, Polyimides, Blackie & Son Ltd., Bishopbriggs, Glasgow, United Kingdom, 1990].
Norbornene terminated polyimides have also been known for many years [H. R. Lubowitz, U.S. Pat. No. 3,528,950 (1970)]. The norbornene group reacts to form thermo-oxidatively stable polyimides which have found use as high temperature composite matrix resins [D. Wilson, H. D. Stenzenberger and P. M. Hergenrother, Polyimides, Blackie & Son Ltd., Bishopbriggs, Glasgow, United Kingdom, 1990].
A primary object of this invention is to provide polyimides terminated with reactive groups which can be processed at low pressures to provide polyimides with improved solvent resistance, modulus and elevated use temperatures.
Another object of this invention is to provide a polyimide copolymer system that can be processed without the evolution of volatiles, which is melt stable at high temperatures, which has improved adhesive properties, which has improved composite mechanical properties, and which has improved solvent resistance.